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991.
Condić-Jurkić K Perchyonok VT Zipse H Smith DM 《Journal of computational chemistry》2008,29(14):2425-2433
High level ab initio and density functional calculations have been employed to determine the most appropriate manner in which to truncate an arginine-bound carboxylate motif, using the substrate mechanism of Pyruvate Formate-Lyase as a case study. The results show that, both qualitatively and quantitatively, a neutral carboxylic acid provides a more realistic approximation to the salt bridge arrangement than does a bare anionic carboxylate substituent. 相似文献
992.
R. Jaćimović P. Makreski V. Stibilj T. Stafilov 《Journal of Radioanalytical and Nuclear Chemistry》2008,278(3):795-799
Major and trace element contents in iron ore reference materials were investigated using k
0-instrumental neutron activation analysis (k
0-INAA). To avoid iron interferences, radiochemical separation was developed (k
0-RNAA). The determination of the investigated elements in the inorganic phase from hydrochloric acid solution was performed
after radiochemical separation of iron by diisopropyl ether. It was found that after the Fe elimination, the limit of detection
for some elements was much lower that enables their direct determination. The distribution of 39 elements (with intermediate/medium
and long half-life radionuclides) after Fe removal was investigated. 相似文献
993.
Baosić R Radojević A Radulović M Miletić S Natić M Tesić Z 《Biomedical chromatography : BMC》2008,22(4):379-386
The lipophilicity of a series of Schiff base ligands and their complexes with nickel(II) and copper(II) has been determined by reversed-phase thin-layer chromatography using binary dioxane-water mobile phase. Chelate ligands were prepared by condensation of diamine and the corresponding beta-diketone. Copper(II) and nickel(II) complexes with chelate ligands containing ethane-1,2-diamine or propane-1,2-diamine as the amine part and pentane-2,4-dione and/or 1-phenylbutane-1,3-dione, pentane-2,4-dione and/or 1,1,1-trifluoropentane-2,4-dione, or 1,1,1-trifluoropentane-2,4-dione and/or 1-phenylbutane-1,3-dione as the beta-diketone part were synthesized. Some of investigated compounds were screened for their in vitro antifungal activity against Sacharomyces cerevisiae and antibacterial activity against Escherichia coli. Chromatographically obtained lipophilicity parameters were correlated both with calculated n-octanol-water partition coefficient C log P and antimicrobial activities. Satisfactory correlations were obtained. Chromatographic data proved to be reliable parameters for describing the lipophilic properties of the investigated compounds. Additionally, the principal components analysis was performed on the data chromatographically obtained. This statistical method was useful for distinguishing compounds and objective comparison of their lipophilicity parameters. 相似文献
994.
Tomislav P. Živković 《Journal of mathematical chemistry》2008,43(2):518-600
Interaction of a finite quantum system that contains ρ eigenvalues and eigenstates with an infinite quantum system that contains a single one-parameter eigenvalue band is considered. A new approach for the treatment of the combined system
is developed. This system contains embedded eigenstates with continuous eigenvalues , and, in addition, it may contain isolated eigenstates with discrete eigenvalues . Two ρ × ρ eigenvalue equations, a generic eigenvalue equation and a fractional shift eigenvalue equation are derived. It is shown that all properties of the system that interacts with the system can be expressed in terms of the solutions to those two equations. The suggested method produces correct results, however
strong the interaction between quantum systems and . In the case of the weak interaction this method reproduces results that are usually obtained within the formalism of the
perturbation expansion approach. However, if the interaction is strong one may encounter new phenomena with much more complex
behavior. This is also the region where standard perturbation expansion fails. The method is illustrated with an example of
a two-dimensional system that interacts with the infinite system that contains a single one-parameter eigenvalue band. It is shown that all relevant completeness relations are satisfied,
however strong the interaction between those two systems. This provides a strong verification of the suggested method. 相似文献
995.
Połeć-Pawlak K Abramski JK Ferenc J Foteeva LS Timerbaev AR Keppler BK Jarosz M 《Journal of chromatography. A》2008,1192(2):323-326
Varying the counter-ion is a highly supportive practice in tackling the problem of poor water-solubility of metal complexes of pharmaceutical importance. As a matter of fact, the relevant structural modification may alter the metabolic pathways and possibly the mode of action of a drug. To prove that this does not take place for one of the lead anticancer metal-based developmental compounds, indazolium trans-[RuCl(4)(1H-indazole)(2)] (KP1019), its reactivity toward human serum proteins was assessed under simulated physiological conditions and compared to that of a much more soluble analogue, sodium trans-[RuCl(4)(1H-indazole)(2)] (KP1339). For such kinetic assaying, capillary electrophoresis (CE) interfaced online with inductively coupled plasma mass spectrometry (ICP-MS) to specifically monitor changes in the metal speciation following the formation of ruthenium-protein adducts was applied. The rate constants of interaction with albumin and transferrin were determined at pharmacologically fitting drug-to-protein ratios as on average 0.0319+/-0.0021 min(-1) and 0.0931+/-0.0019 min(-1) (KP1019) and 0.0316+/-0.0018 min(-1) and 0.0935+/-0.0053 min(-1) (KP1339), respectively. The results of this brief study showed that changing from organic to inorganic counter-ion at the stage of formulation could commonly be recommended for improving ruthenium-based drug solubility and bioavailability. 相似文献
996.
A set of mass-weighted internal coordinates was derived and applied to the double proton transfer reaction in the formic acid dimer (FAD). The coordinate set was obtained starting from the Hirschfelder "mobile" by an optimization procedure consisting of a sequence of kinematic rotations. In FAD, the optimization procedure leads to three coordinates that do change significantly along the reaction path. These coordinates span the reaction space, whereas the remaining modes are treated in a harmonic approximation. The effect that the dimer dissociative motion has on the ground and excited vibrational states dynamics was explored. In the frequency region corresponding to the symmetric OH-stretch vibration four doublets have been identified with splittings of 2.76, 0.07, 0.60, and 4.03 cm(-1). 相似文献
997.
Yan Z McCracken T Xia S Maslak V Gallucci J Hadad CM Badjić JD 《The Journal of organic chemistry》2008,73(2):355-363
The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1syn in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1syn in a moderate 30% yield. The reaction diastereoselectivity is affected by the concentration of Cu(I) and Cs+: increasing quantities of the cations enhanced the syn/anti ratio of the isolated cyclotrimer from statistical (1:3) to a more desirable (4.5:1) ratio, in favor of the molecular bowl 1syn. 1H NMR spectroscopic studies suggested the coordinating affinity of 1syn toward transition metals Cu(I), Ag(I), and Au(I), to account for the observed templation effect. In particular, the tridentate 1syn has been shown to bind to one Ag(I) cation in the assembly process that is driven with enthalpy (Delta H degrees = -19 +/- 2 kcal/mol, Delta S degrees = -45 eu). The complete coordination was not cooperative, and was hypothesized to be impeded with the adverse entropy. Accordingly, density functional theory (BP86) calculations of 1syn and its mono-, bis-, and tris-Ag(I) complexes suggested that the coordination of one to three silver cations is highly exothermic. The calculations also revealed that the bowl constriction is necessary for the aromatic arms to become preorganized and bind to a silver cation(s) (Delta E approximately 8 kcal/mol). Ultimately, Ag(I) has been shown to assist the diastereoselective formation of 1syn, lending support to the notion of template-directed synthesis. 相似文献
998.
Ljiljana S. Vojinović-Ješić Goran A. Bogdanović Vukadin M. Leovac Valerija I. Češljević Ljiljana S. Jovanović 《Structural chemistry》2008,19(5):807-815
Abstract The monoligand complexes of the formula M(HPLGT)(NCS)2 (M = Cu(II), Zn(II)) in which the ligand tridentate ONO pyridoxilidene Girard-T hydrazone, [H3PLGT]Cl2 · 2H2O, was coordinated in neutral doubly deprotonated form were synthesized. Also, the first complexes with the ligand coordinated
in triply deprotonated monoanionic form of the formula [Cu(PLGT)N3] and [Co(PLGT)(NO2)2NH3] · 3H2O are reported. The single crystal X-ray analysis of [Cu(HPLGT)(NCS)2] showed that Cu(II) is placed in a square-pyramidal surrounding consisting of one tridentate Schiff base and one NCS group
in the basal plane and the other NCS group in the apical position. Intermolecular hydrogen bonds leading to centrosymmetrical
dimerization of these complexes were discussed. In the reaction of Girard-T and Hacac in the presence of CuCl2, a mixture of single crystal complexes of the composition [Cu(3,5-Me2pz)2Cl2]2 and [Cu(acac)2] · 2[Cu(3,5-Me2pz)2Cl2] was obtained and X-ray analysis of the latter one was reported.
Index abstract Crystal structure of the Cu(II) complex with pyridoxilidene Girard-T hydrazone was analyzed. Additional two Cu(II) complexes
obtained by the reaction of Girard-T reagent and Hacac in the presence of CuCl2 were also studied by single crystal X-ray analysis. 相似文献
999.
The results of an ab initio study of the vibronic structure in the a1Deltag electronic state of C2H2++ and its deuterated species (C2D2++) are presented. They are generated employing a simple model that incorporates the minimal number of terms contributing to the Renner-Teller effect. The trans- and cis-bending potential curves at planar nuclear arrangements are obtained by means of large-scale configuration interaction calculations. The corresponding harmonic vibrational frequencies are 717 and 650 cm-1 for C2H2++, and 549 and 477 cm-1 in the case of C2D2++. It is found that the splitting of the potential surfaces is moderate at trans-distortions of linearity, while it is extremely small at cis-bending vibrations. The eigenvalues and eigenfunctions of the model Hamiltonian employed are obtained by means of a perturbative and a variational approach. 相似文献
1000.
Quantum effects in the scattering and desorption process of a water molecule from a graphite surface are investigated using the linearized path integral model. The graphite surface is quantized rigorously using the fully quantum many-body Wigner transform of the surface Boltzmann operator, while the water molecule is treated as rigid. Classical dynamics with these quantized initial conditions show that quantizing the surface at 100 and 300 K results in markedly different results, compared to a fully classical analysis. The trapping probability (defined as the probability of multiple encounters with the surface) is not sensitive to the choice of dynamical treatment, but the residence time on the surface is much shorter in the quantum case. At 300 K the transiently trapped molecules desorb from the surface with a rate constant which is 60-70% larger than the corresponding classical value. Lowering the surface temperature to 100 K decreases the quantum rate constant by approximately a factor of 3 while all trapped molecules stick to the surface in the classical case. The stability of the quantum initial state for the highly anisotropic graphite crystal is discussed in detail as well as the dynamical consequences of energy redistribution during the scattering process. The graphite surface application demonstrates that the Boltzmann operator Wigner transform for a system with 900 degrees of freedom can be obtained by the so-called gradient implementation [Poulsen et al. J. Chem. Theory Comput. 2006, 2, 1482] of the underlying Feynman-Kleinert effective frequency theory, an implementation that only requires a force and potential routine for the system at hand, and hence is applicable to any molecule-surface collision problem. 相似文献